US5593617A - Photochemically polymerizable liquid crystals - Google Patents

Photochemically polymerizable liquid crystals Download PDF

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Publication number
US5593617A
US5593617A US08/517,480 US51748095A US5593617A US 5593617 A US5593617 A US 5593617A US 51748095 A US51748095 A US 51748095A US 5593617 A US5593617 A US 5593617A
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group
phenylcarbonyloxy
ooc
coo
phenylene
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Stephen Kelly
Teodor Luk ac
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Rolic Technologies Ltd
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Hoffmann La Roche Inc
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Assigned to HOFFMAN-LA ROCHE INC. reassignment HOFFMAN-LA ROCHE INC. ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: F. HOFFMAN-LA ROCHE AG
Assigned to ROLIC AG reassignment ROLIC AG ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: HOFFMANN-LA ROCHE INC.
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
    • C07C69/76—Esters of carboxylic acids having a carboxyl group bound to a carbon atom of a six-membered aromatic ring
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00—Liquid crystal materials
    • C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
    • C09K19/06—Non-steroidal liquid crystal compounds
    • C09K19/08—Non-steroidal liquid crystal compounds containing at least two non-condensed rings
    • C09K19/10—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings
    • C09K19/20—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings linked by a chain containing carbon and oxygen atoms as chain links, e.g. esters or ethers
    • C09K19/2007—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings linked by a chain containing carbon and oxygen atoms as chain links, e.g. esters or ethers the chain containing -COO- or -OCO- groups
    • C09K19/2014—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings linked by a chain containing carbon and oxygen atoms as chain links, e.g. esters or ethers the chain containing -COO- or -OCO- groups containing additionally a linking group other than -COO- or -OCO-, e.g. -CH2-CH2-, -CH=CH-, -C=C-; containing at least one additional carbon atom in the chain containing -COO- or -OCO- groups, e.g. -(CH2)m-COO-(CH2)n-
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
    • C07C69/76—Esters of carboxylic acids having a carboxyl group bound to a carbon atom of a six-membered aromatic ring
    • C07C69/84—Esters of carboxylic acids having a carboxyl group bound to a carbon atom of a six-membered aromatic ring of monocyclic hydroxy carboxylic acids, the hydroxy groups and the carboxyl groups of which are bound to carbon atoms of a six-membered aromatic ring
    • C07C69/92—Esters of carboxylic acids having a carboxyl group bound to a carbon atom of a six-membered aromatic ring of monocyclic hydroxy carboxylic acids, the hydroxy groups and the carboxyl groups of which are bound to carbon atoms of a six-membered aromatic ring with etherified hydroxyl groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
    • C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
    • C08F20/10—Esters
    • C08F20/26—Esters containing oxygen in addition to the carboxy oxygen
    • C08F20/30—Esters containing oxygen in addition to the carboxy oxygen containing aromatic rings in the alcohol moiety
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00—Liquid crystal materials
    • C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
    • C09K19/38—Polymers
    • C09K19/3833—Polymers with mesogenic groups in the side chain
    • C09K19/3842—Polyvinyl derivatives
    • C09K19/3852—Poly(meth)acrylate derivatives
    • C09K19/3871—Poly(meth)acrylate derivatives containing amino acid derivatives

Definitions

  • the present invention is related to photochemically polymerizable liquid crystal compounds, liquid crystalline mixtures which contain such compounds, and the use of the liquid crystal compounds in a cross-linked state as optical or electronic components.
  • Liquid crystals having at least two photochemically polymerizable groups can be orientated on a substrate or in a cell, for example by orientating layers or in a field. These orientated liquid crystals, provided with a suitable mount of a photoinitiator, are polymerized by irradiation with light of a suitable wavelength. The cross-linked structure which is thereby produced remains even at high temperatures.
  • Such layers can be found, for example as, parts of hybrid layers as described in Swiss Patent Applications CH 2016/94 and CH 2017/94.
  • optical components such as retarders, wave guides, optical grids and filters, integrated color filters or cells with piezoelectric and with non-linear optical (NLO) properties can be prepared. These types of optical components can be used, for example, in projection systems.
  • networks for optical retarders should have a high birefringence in order to keep the layer thickness of the integrated optical component to a minimum.
  • Polymers which are electrically insulating, but which have a good thermal conductivity, are used in microelectronics to rapidly and efficiently disperse heat which is formed when a high density of components is operated. There is also a need for insulating layers having a low dielectric constant and a high heat resistance. Homogeneously orientated liquid crystalline networks are advantageous for such applications by virtue of their low thermal expansion coefficients, high thermal conductivity and stability.
  • liquid crystals for optical and electrical components
  • these liquid crystalline materials are also suitable for cladding glass fibers for optical data transmission.
  • the use of such networks increases the elastic modulus in the longitudinal axis of the fiber, lessens the thermal expansion coefficient and reduces microdistortion losses. This leads to an increased mechanical stability.
  • liquid crystals are usually used as mixtures of several components, it is important that the components have a good miscibility with one another.
  • Conventional photochemically polymerizable liquid crystals usually have a high melting point and clearing point.
  • a spontaneous thermal polymerization can occur prematurely in the processing, which is carried out at temperature barely below the clearing point, because at this temperature the viscosity in the liquid crystalline state is at its lowest and is therefore favorable for a good orientatability.
  • This spontaneous polymerisation leads to the formation of domains, whereby the optical and thermal properties in the cross-linked layers produced can be clearly influenced.
  • the melting point can be decreased by producing complicated mixtures with several components, which indeed permits a processing at lower temperatures, but brings with it the danger of a crystallization of conventional polymerizable liquid crystals.
  • photochemically polymerizable compounds having low melting points and clearing points so that they can be processed very readily at temperatures above room temperature in the liquid crystalline state and also in solution.
  • a further object of the present invention is to produce photochemically polymerizable compounds that can be orientated and structured without forming domains.
  • An additional object of the present invention is to produce polymerizable compounds which are thermally stable and have long term stability in the crosslinked state.
  • the present invention provides compounds which are suitable as components of liquid crystal mixtures. These compounds have the general formula ##STR2## wherein A 1 , A 2 and A 3 are, independently, photochemically polymerizable mesogenic residues.
  • the mesogenic photochemically polymerizable residues A 1 , A 2 and A 3 can be different or the same. These mesogenic residues are provided terminally with a polymerizable residue that makes them suitable for the above-stated objectives.
  • the present invention provides compounds which are outstandingly suitable as components of liquid crystal mixtures. These compounds have the general formula ##STR3## wherein A 1 , A 2 and A 3 are, independently, photochemically polymerizable mesogenic residues.
  • the mesogenic photochemically oligomerizable or polymerizable residues A 1 , A 2 and A 3 can be different or the same.
  • Mesogenic residues are known to persons skilled in the art and are described, for example, in "Flussigkristalle in Tabellen” Vol. II, Deutscher Verlag fur Grundstoffindustrie, Leipzig, 1984. These mesogenic residues of the present invention are provided terminally with a polymerizable residue.
  • the compounds of general formula I have a good solubility in usual solvents, for example, in anisole, N,N'-dimethylacetamide or N-methylpyrrolidone and are distinguished by a relatively low viscosity. They can therefore be applied to a suitable surface without difficulty, usually by spin-coating. Moreover, since the compounds of the present invention have a liquid crystalline phase, they can be directed, prior to the cross-linking, on an orientating layer or by applying an electric or magnetic field.
  • Preferred compounds of formula I are those in which the photochemically oligomerizable or polymerizable mesogenic residues A 1 , A 2 and A 3 are, independently, residues of the formula ##STR4## wherein C and D are, independently, selected from the group consisting of pyridine-2,5-diyl, pyrimidine-2,5-dyl, trans-1,4-cyclohexylene, trans-1,3-dioxane-2,5-dyl and 1,4-phenylene, which phenylene may be substituted with one or more nitro, acetyl, halogen, methyl and cyano;
  • Z1 is selected from the group consisting of a single bond, --CH 2 CH 2 --,--CH 2 O--,--COO--,--OOC--,--(CH 2 ) 4 -- and --(CH 2 ) 3 O--;
  • Z 2 is selected from the group consisting of a single bond, --CH 2 CH 2 --, --CH 2 O--, --OCH 2 --, --COO--, --OOC--, --(CH 2 ) 4 --, --O(CH 2 ) 3 -- and --(CH 2 ) 3 O--;
  • Z 3 is selected from the group consisting of --(CY 2 ) m --, --(CY 2 ) m O--, --(CY 2 ) m COO--, --(CY 2 ) m OOC, --(Si[(CH 3 ) 2 ]O) p --, --OCH 2 (Si[(CH 3 ) 2 ]O) p Si[(CH 3 ) 2 ]CH 2 O-- and --NHCH 2 (Si[(CH 3 ) 2 ]O) p Si[(CH 3 ) 2 ]CH 2 NH--;
  • Y is hydrogen or fluorine
  • m is a whole number of 1 to 16;
  • p is a whole number of 1 to 16;
  • n 0 or 1
  • R 1 is a polymerizable group selected from the group consisting of acrylate, allyl ether, allyl ester, methacrylate, 2-chloroacrylate, 2-phenylacrylate, acryloylphenylene, acrylamide, methacrylamide, 2-phenylacrylamide, epoxy, itaconic acid ester, vinyl ether, vinyl ester, styrene derivative, maleic acid derivative and fumaric acid derivative; or a dimerizable group selected from the group consisting of chalcone and a cinnamic acid derivative which may be substituted with one or more methyl, methoxy, cyano and halogen.
  • preferred 1,4-phenylene which may be substituted with one or more nitro, acetyl, halogen, methyl and cyano include 1,4-phenylene, 2-nitro-1,4-phenylene, 3-nitro-1,4-phenylene, 2-acetyl-1,4-phenylene, 3-acetyl-1,4-phenylene, 2-fluoro-1,4-phenylene, 3-fluoro-1,4-phenylene, 2,3-difluoro-1,4-phenylene, 2-chloro-1,4-phenylene, 3-chloro-1,4-phenylene, 2,3-dichloro-1,4-phenylene, 2-cyano-1,4-phenylene, 3-cyano-1,4-phenylene, 2,3-dicyano-1,4-phenylene, 2-methyl-1,4-phenylene or 3-methyl-1,4-phenylene.
  • Z 1 and Z 11 are, independently, selected from the group consisting of a single bond, --CH 2 CH 2 --, --CH 2 O--, --COO--, --OOC--, --(CH 2 ) 4 -- and --(CH 2 ) 3 O--;
  • Z 2 and Z 21 are, independently, selected from the group consisting of a single bond, --CH 2 CH 2 --, --CH 2 O--, --OCH 2 --, --COO--, --OOC--, --(CH 2 ) 4 --, --O(CH 2 ) 3 -- and --(CH 2 ) 3 O--;
  • Z 3 and Z 31 are, independently, selected from the group consisting of --(CY 2 ) m --, --(CY 2 ) m O--, --(CY 2 ) m COO--, --(CY 2 ) m OOC, --(Si[(CH 3 ) 2 ]O) p --, --OCH 2 (Si[(CH 3 ) 2 ]O) p Si[(CH 3 ) 2 ]CH 2 O-- and --NHCH 2 (Si[(CH 3 ) 2 ]O) p- Si[(CH 3 ) 2 ]CH 2 NH--;
  • Y is hydrogen or fluorine
  • m is a whole number of 1 to 16;
  • p is a whole number of 1 to 16;
  • n 0 or 1
  • R 1 and R 11 are, independently, a polymerizable group selected from the group consisting of acrylate, allyl ether, allyl ester, methacrylate, 2-chloro-acrylate, 2-phenylacrylate, acryloylphenylene, acrylamide, methacrylamide, 2-phenylacrylamide, epoxy, itaconic acid ester, vinyl ether, vinyl ester, styrene derivative, maleic acid derivative and fumaric acid derivative; or a dimerizable group selected from the group consisting of chalcone and a cinnamic acid derivative which may be substituted with one or more methyl, methoxy, cyano and halogen.
  • Most particularly preferred compounds of formula I are those in which the mesogenic residues A 1 , A 2 and A 3 are the same, and are compounds of the formula ##STR6## wherein R 1 , Z 3 , Z 2 , Z 1 and n have the aforementioned significances.
  • the mesophase type of the compounds of the present invention can be influenced by varying the rings C or C 1 and D or D 1 .
  • Heterocyclic rings tend to produce smectic phases, while phenylene and cyclohexylene rings promote nematic tendencies.
  • rings C or C 1 and D or D 1 are, independently, selected from the group consisting of 1,4-phenylene, 2-fluoro-1,4-phenylene, 3-fluoro-1,4-phenylene, pyridine-2,5-diyl and pyrimidine-2,5-diyl, and especially preferred, are selected from the group consisting of 1,4-phenylene, 2-fluoro-1,4-phenylene and 3-fluoro-1,4-phenylene.
  • Especially preferred compounds of formulae I-1 to I-4 are compounds in which Z 1 and Z 11 are, independently, selected from the group consisting of --CH 2 O--, --COO-- and--OOC--; Z 2 and Z 21 are, independently, selected from the group consisting of a single bond, --CH 2 CH 2 --, --CH 2 --, --OCH 2 --, --COO-- and--OOC--; and Y is hydrogen.
  • the residues R 1 and R 11 are, independently, acrylate, methacrylate, 2-chloroacrylate, 2-phenylacrylate, acryloylphenylene, acrylamide, methacrylamide, 2-phenylacrylamide, epoxy, vinyl ether, vinyl ester, styrene derivative, maleic acid derivative and fumaric acid derivative; acrylate, methacrylate, vinylether and epoxy are quite especially preferred.
  • Z 32 is selected from the group consisting of --(CH 2 ) t --, --(CH 2 ) t O--, --(CH 2 ) t COO-- and --(CH 2 ) t OOC--; t is a whole number of 3 to 12;
  • C 2 is selected from the group consisting of 1,4-phenylene, 2-fluoro-1,4-phenylene and 3-fluoro-1,4-phenylene;
  • Z 12 is selected from the group consisting of --CH 2 O--, --COO-- and --OOC--.
  • the compounds of the present invention having the general formulae I, I-1, I-2 and I-3, in which the mesogenic residues A 1 , A 2 and A 3 are different from one another are very readily synthesized and can be produced according to known methods, for example analogously to the methods illustrated in Schemes 1 to 3 and in the Examples.
  • the mesogenic residues of formulae II and II-a are known or are analogs of known structures and can be prepared by known methods and subsequently linked with the aromatic ring.
  • the compounds of formula I can be used as single compounds or in the form of mixtures with one another or with other liquid crystal components.
  • the liquid crystalline mixtures of the present invention contain at least two components, at least one of which component is a compound of formula I.
  • a second component and any other additional components can comprise compounds of formula I or other known liquid crystal compounds with or without photo-crosslinkable groups.
  • One or more chiral compounds can also be present in the mixture.
  • the content of different compounds of formula I in the liquid crystal mixtures of the present invention can be as high as 100 wt. %.
  • the mixtures in accordance with the present invention in addition to one or more compounds of formula I, contain one or more compounds from the group of compounds of the general formulae as described in Swiss Patent Application CH 953/94: ##STR11## wherein t is a whole number of 3 to 12;
  • q is a whole number of 2 to 12;
  • X is selected from the group consisting of hydrogen, fluorine, and chlorine; or lower alkyl such as methyl, ethyl, propyl or butyl.
  • C is a crystalline phase
  • S is a smectic phase
  • N is a nematic phase
  • I is the isotropic phase.
  • N,N'-dicyclohexylcarbodiimide 0.2 g is added at room temperature while stirring to a solution of 0.6 g of 2,5-bis(4-[6-acryloyloxyhexyloxy]-phenylcarbonyloxy)-benzoic acid, 0.4 g [4-(4-[6-acryloyloxyhexyloxy]-phenylcarbonyloxy)phenyl]methanol and 0.04 g of 4-dimethylaminopyridine in 20 ml of dichloromethane. The reaction mixture is stirred at room temperature overnight, poured into 100 ml of water and then extracted three times with 50 ml of dichloromethane each time.
  • IRGACURE a photoinitiator
  • the glass plate had previously been coated with methacryloyloxyethyl 3-(E)-[4-cyano4'-biphenyl]acrylate and then irradiated with linear polarized light.
  • a predetermined structure was inscribed photolithographically by means of a mask in the photoorientable polymer network layer (PPN layer).
  • the spun-on new layer (on the PPN layer) was dried at 90° C. on a heating block, then irradiated with xenon light in a vacuum oven under a vacuum at 90° C.
  • the inscribed original structure remained and was copied faithfully by the new network.
  • a dear double refraction (Dn) was recognizable. This layer functions as a structural optical retarder.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Engineering & Computer Science (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Medicinal Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Proteomics, Peptides & Aminoacids (AREA)
  • Polymers & Plastics (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Liquid Crystal Substances (AREA)
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US08/517,480 1994-09-12 1995-08-21 Photochemically polymerizable liquid crystals Expired - Fee Related US5593617A (en)

Applications Claiming Priority (2)

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CH2771/94 1994-09-12
CH277194 1994-09-12

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US (1) US5593617A (ko)
EP (1) EP0700981B1 (ko)
JP (1) JP3973707B2 (ko)
KR (1) KR100391530B1 (ko)
CN (1) CN1091795C (ko)
DE (1) DE59508919D1 (ko)
HK (1) HK1011043A1 (ko)
SG (1) SG38876A1 (ko)

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US5705096A (en) * 1995-03-15 1998-01-06 Alps Electric Co., Ltd. UV crosslinking compound, alignment film for LCD component and LCD component
US5707544A (en) * 1995-06-07 1998-01-13 Rolic Ag Chromophore-containing photo cross-linkable liquid crystals
US6090308A (en) * 1995-02-06 2000-07-18 Merck Patent Gesellschaft Direactive mesogenic compounds and intermediates
US6171518B1 (en) * 1997-04-29 2001-01-09 U.S. Philips Corporation Method of preparing a cross-linked macroscopically oriented polymer
US6395351B1 (en) 1997-05-22 2002-05-28 Rolic Ag Polymerisable liquid crystalline compounds
US20030160210A1 (en) * 2001-12-27 2003-08-28 Merck Patent Gmbh Polymerisable monocyclic compounds
US6630076B1 (en) 1998-08-07 2003-10-07 Rolic Ag Liquid crystalline compounds
US6676851B1 (en) * 1999-02-17 2004-01-13 Rolic Ag Laterally substituted curable liquid crystals
US6733690B1 (en) * 1999-03-17 2004-05-11 Rolic Ag Laterally substituted curable liquid crystals
US6746729B1 (en) * 1999-04-19 2004-06-08 Rolic Ag Liquid crystal compounds
US20060035034A1 (en) * 2001-11-13 2006-02-16 Huntsman Advance Materials Americas Inc. Production of composites articles composed of thin layers
US20080081133A1 (en) * 2006-09-21 2008-04-03 Chisso Corporation Trifunctional compound, composition and polymer thereof
US20100266821A1 (en) * 2007-12-21 2010-10-21 Rolic Ag Functionalized photoreactive compounds
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US20110017838A1 (en) * 2008-03-11 2011-01-27 Rolic Ltd. Optical biometric security element
US20110068493A1 (en) * 2009-09-22 2011-03-24 Kent State University Stimuli responsive liquid crystal-polymer composite fibers
US20110147657A1 (en) * 2009-12-22 2011-06-23 Chisso Corporation Polymerizable liquid crystal compound, polymerizable liquid crystal composition and anisotropic polymer
US20110186777A1 (en) * 2008-10-01 2011-08-04 Zeon Corporation Polymerizable chiral compound, polymerizable liquid crystal composition, liquid crystal polymer and optically anisotropic body
US8883271B2 (en) 2010-03-31 2014-11-11 Zeon Corporation Polymerizable chiral compound, polymerizable liquid crystal compound, liquid crystal polymer and optically anisotropic body
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EP0700981A3 (ko) 1996-03-27
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KR960010608A (ko) 1996-04-20

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